Shaded Zirconium Oxide Articles

ABSTRACT

A dental article includes yttria stabilized tetragonal zirconia polycrystalline ceramic, and no more than about 0.15 wt. % of one or more coloring agents of one or more of: Pr, Tb, Cr, Nd, Co, oxides thereof, and combinations thereof, whereby the dental article is provided with a color corresponding to a natural tooth shade; and wherein the dental article has a flexural strength of at least about 800 MPa. Corresponding methods are also described.

This application is a divisional application of U.S. application Ser.No. 11/717,199, filed Mar. 13, 2007, which claims priority under 35U.S.C. §119 to U.S. Patent Application Ser. No. 60/789,610 filed Apr. 6,2006, all of which are incorporated by reference herein.

BACKGROUND

In the discussion of the state of the art that follows, reference ismade to certain structures and/or methods. However, the followingreferences should not be construed as an admission that these structuresand/or methods constitute prior art. Applicant expressly reserves theright to demonstrate that such structures and/or methods do not qualifyas prior art.

Yttria Tetragonal Zirconia Polycrystalline (YTZP) materials have emergedas a high-strength framework material for dental prostheses(single-units up to multiple unit bridges). However due to its inherentwhite color, often the esthetics of the finished restoration is inferiorto what is achievable with other all-ceramic systems.

Currently there are two predominant commercially available methods todeal with the stark white color of zirconia. In the one method, thecolor of the zirconia is “hidden” by applying either a layer of stain orliner. The other method entails shading the zirconia by immersion in, orpainting with, coloring solutions while in the pre-sintered state.Coloring with a stain and/or applying a liner involves an extrafabrication step and lowers translucency. Shading with a coloringsolution similarly requires the extra step of dipping or painting, andextra time to dry before sintering. Also, this method is deficient asthe color of the final sintered framework often is not uniform.

An alternative method is to use porous zirconia blocks that arepreshaded to the desired coloration. Such blocks only need to be firedafter any machining, thus eliminating the coloring with solutions step.As the fully sintered frameworks emerge from the furnace already shaded,the stain/liner step can be eliminated. Additionally, the color of thesintered frameworks is characteristically uniform, which is anotheradvantage over the shading with coloring solution method.

A finished dental restoration should match the color of the patient'steeth, i.e., it should be “tooth colored”. The colors of human teethappear to range from a light almost white-tan to a light brown, andoccupy a very specific color space. This color space can be described bythe commonly used CIE (Commission Internationale de l'Eclariage) L*, a*,b* conventions, which represents colors in a three-dimensional Cartesiancoordinate system. L*, or “value”, is a measure of luminance orlightness, and is represented on the vertical axis. The a*, b*coordinates, are a measure of chromaticity and are represented on thehorizontal coordinates, with positive a* representing red and negativea* representing green, and positive b* representing yellow and negativeb* representing blue. U.S. Pat. No. 6,030,209, which is incorporatedherein by reference, presents the CIE L*, a*, b* color coordinates oftooth colors represented by the Vita Lumen® shade guide systemmanufactured by Vita Zahnfabrik (i.e., it presents the color space oftooth colors). Herein, “tooth color” is taken to mean CIE L*, a*, b*color coordinates that fall within, or very close to, this color space.

U.S. Pat. No. 6,713,421 appears to describe yttria-stabilized zirconiadental milling blanks that are formed with 0-1.9 wt. % coloringadditives. The composition described therein includes 0.1 to 0.50 wt. %of at least one oxide of aluminum, gallium, germanium and indium for thepurpose of lowering the sintering temperature and increasing stabilityand hydrolytic resistance in the densely sintered state. However, theaddition of aluminum oxide (alumina) to zirconia also often results indiscrete alumina inclusions distributed throughout the microstructure.This occurs in part due to the low solubility of alumina in zirconia.Further, it presents a particular disadvantage for dental applicationsbecause alumina inclusions can lower the translucency of the zirconiasince the refractive index of alumina, 1.77, differs considerably fromthat of tetragonal zirconia, 2.16. Thus, it is desirable that dentalzirconia is devoid of any alumina inclusions. A means to achieve this isto minimize, or eliminate, the alumina addition, thereby minimizing thepotential for the alumina inclusions in the final microstructure.

In U.S. Pat. No. 6,713,421 the blanks are made from powders or granulesthat have been doped with the various oxides via a solution followed bya co-precipitation method. The cited advantage of this method is thatthe various oxides are distributed homogeneously throughout the powder.However, the field of dental restoratives requires many shades (e.g., 7zirconia core shades as per LAVA, 16 Vita Classic shades, etc.), andhaving to prepare so many individually shaded powders or granules can becost-prohibitive.

Yet another disadvantage of U.S. Pat. No. 6,713,421 is that it requiresrelatively large amounts of the preferred coloring oxides, iron oxideand erbium oxide. This is revealed by the Preparation Example 1 citedwhich teaches adding 0.2 wt. % iron oxide+0.38 erbium oxide (0.58%total) to color 3YTZP. Although the patent does not indicate if thisresulted in a tooth color, it can be inferred from U.S. Pat. No.5,219,805, which appears to disclose coloration of yttria-stabilizedzirconia for dental bracket applications using combinations of Fe₂O₃,Er₂O₃, and Pr₆O₁₁, that even higher Fe₂O₃ and Er₂O₃ concentrations arenecessary to achieve tooth coloration. For instance, according to theexamples given in U.S. Pat. No. 5,219,805, up to 1.0 mol % Er₂O₃ (3.0wt. %) additive is required to achieve dental brackets “having colortone similar to ivory-colored teeth”. Additionally, up to 0.2 mol %Fe₂O₃ (0.25 wt. %) is required to achieve tooth colors, which althoughless than the 1 mol % Er₂O₃ required, is a considerable amount. As suchquantities are significant, they can have a negative effect on otherproperties of the resulting YTZP cores, such as on strength, weibullmodulus, hydrolytic resistance, and grain size.

Additionally, it has been observed that Er₂O₃ additions to 3Y-zirconia,of 0.2 wt. % or greater, results in sintered bodies that fluoresce adark yellow under ultraviolet (UV) lighting. This is inappropriate for adental framework, which under UV, ideally, should fluoresce bluish-whiteto mimic that of natural teeth. Less ideally, the framework should notfluoresce at all in the visible light range. In the latter casefluorescence is typically imparted to the final restoration by theoverlay porcelains. The shortcoming of an inappropriate fluorescence isovercome by the present invention.

The prior art also shows Cr additions result in green or browncoloration. For example, U.S. Pat. No. 3,984,524 appears to describeolive coloration of cubic zirconia with addition of 0.1 to 2 wt. %Cr₂O₃, U.S. Pat. No. 4,742,030 appears to describe green coloration of 5mol % yttria-stabilized zirconia with addition of 0.7 wt. % Cr₂O₃, andbrown coloration with addition of 0.2 wt. % Cr₂O₃, respectively.

French patent publication 2,781,366 and Cales et. al. (“Colored ZirconiaCeramics for Dental Applications,” Bioceramics Vol. 11, edited by R. Z.LeGeros and J. R. LeGeros; Proceedings of the 11th InternationalSymposium on Ceramics in Medicine; York, N.Y.; November 1998) appear toidentify a number of colorants, and was reportedly successful inachieving some of the Vita shades in 3YTZP by using combinations ofFe₂O₃, CeO₂ and Bi₂O₃. However, their choice of colorant oxides is adrawback as they are required in fairly large amounts to achieve some ofthe desired shades.

U.S. Pat. No. 5,656,564 appears to teach coloration of zirconia fordental bracket applications using with combinations of Er₂O₃ and Pr₆O₁₁.The sintered zirconia-based ceramic is produced by a procedure generallyincluding combining constituents in solution, precipitating, calcining,pressing, and sintering.

U.S. Pat. No. 5,011,403 appears to describe coloration of zirconiadental brackets using combinations of one or more of oxides of Fe, Niand Mn added to a Zr-based powder.

U.S. Pat. No. 6,709,694 appears to describe the use of solutions forcoloring of pre-sintered zirconia dental frameworks by immersion,painting or spraying using a metal ion coloring solution or metalcomplex coloring solution that is applied to a presintered ceramic,followed by sintering to form a translucent, colored dental ceramic. Theclaimed ions or complexes are of the rare earths elements or subgroupsII and VIII, with an action time of under two hours, and maximumpre-sintered zirconia diameter and height of 10 and 7 mm, respectively.However, this method is not ideal as the color of the final sinteredframeworks often are not uniform and the process requires the extrasteps of applying the solutions and drying prior to sintering.

The development of pink coloration in zirconia by Er additions isdescribed in (i) P. Duran, P. Recio, J. R. Jurado, C. Pascual and C.Moure, “Preparation, Sintering, and Properties of TranslucentEr₂O₃-Doped Tetragonal Zirconia,” J. Am. Ceram. Soc., vol. 72, no. 11,pp. 2088-93, 1989; and (ii) M. Yashima, T. Nagotome, T. Noma, N.Ishizawa, Y. Suzuki and M. Yoshimura, “Effect of Dopant Species onTetragonal (t′)-to-Monoclinic Phase Transformation of Arc-MeltedZrO₂—RO_(1.5) (R=Sm, Y, Er, and Sc) in Water at 200° C. and 100 MPaPressure,” J. Am. Ceram. Soc., no. 78, no. 8, pp. 2229-93, 1989.Additions of CoO, Fe₂O₃ and Cr₂O₃ combinations to yttria-stabilizedzirconia are known to impart a blue color in the final sintered zirconiabodies, as apparently described in Japanese patent publication2,145,475. Additions of one or both of the colorants, Ni oxide andCobalt oxide, to yttria-stabilized zirconia have been shown to result ina purplish colored sintered body, as apparently described in U.S. Pat.No. 5,043,316.

Japanese patent publication 3,028,161 appears to describe thepreparation of colored zirconia by the steps of: (1) mixing zircon-basedpigment with partially stabilized zirconia containing Y₂O₃, MgO, etc.,(2) molding and (3) sintering to provide a colored zirconia sinteredproduct.

Many of the aforementioned coloring additions can negatively affect notonly mechanical properties, including strength and fracture toughness,but also isotropic shrinkage and final sintered density. This can happenfor a number of reasons including: (1) loss of fracture toughness from alowering of the “transformation toughening” effect as a result of theover-stabilization of the tetragonal phase by the additive (eitherchemically, or by grain size reduction) thereby hindering thetransformation from the metastable tetragonal phase to monoclinic phasethat is necessary for the toughening to happen, (2) loss of strength dueto spontaneous microcrack formation that can result if grains grow toolarge because of the additive, and, (3) loss of strength due to theformation of strength-limiting pores in the microstructure due to theadditive. This last reason is what Shah et al. (K. C. Shah, I. Denry andJ. A. Holloway, “Physical Properties of Cerium-Doped TetragonalZirconia,” Abstract 0080, Journal of Dental Research, Vol. 85, SpecialIssue A, 2006) attribute the significant loss of strength, down to275±67 MPa, for 3YTZP materials that were colored using Ce salts.Additionally, they observed that strength decreased linearly with theconcentration of the coloring additive, Ce.

The problem of formation of coarse pores, along with grain growth, incolored zirconia sintered compacts has also been recently recognized inJP 2005289721.

It is also important to recognize that only certain combinations ofcoloring agents in certain proportions will enable the matching of thecolor of a dental article so as to match the desired natural toothcolor, e.g., A, B, C, D of the Vita classic shade guide, and Chromoscop®universal shade guide.

Thus, it would be extremely beneficial to have pre-shaded YTZP blocks orblanks that sinter isotropically to full density and that yield therequired variety of shades consistently and without compromise instrength, fracture toughness, and reliability or Weibull modulus.

SUMMARY

The present invention provides compositions and methods that canoptionally address one or more of the abovementioned shortcomingsassociated with conventional technology, and provide shaded ZrO₂-basedarticles that sinter isotropically to full density, and possess at leastadequate strength, fracture toughness, and a reliability or Weibullmodulus >10 as required per the ASTM Standard for biomedical grade3YTZP. The amount of coloring agent(s) contained in the ZrO₂-basedarticles can be relatively low, thereby minimizing any negative impacton the properties of the articles due to the presence of coloringagent(s) in the composition.

According to one aspect, the present invention provides a dentalarticle; wherein the article may comprise a blank or block, a coping orframework for a dental restoration or implant, or an abutment; thearticle comprising: yttria stabilized tetragonal zirconia; and no morethan about 0.15 wt. % of one or more coloring agents comprising one ormore of: Pr, Tb, Cr, Nd, Co, oxides thereof, and combinations thereof,whereby the dental article is provided with a color corresponding to anatural tooth shade; wherein the dental article has a flexural strengthof at least about 800 MPa when sintered to at least 98% of itstheoretical density.

According to another aspect, the present invention provides a dentalrestoration comprising: (i) a core or framework, and (ii) an overlay.The core or framework comprising yttria stabilized tetragonal zirconia,and no more than about 0.15 wt. % of one or more coloring agentscomprising one or more of: Pr, Tb, Cr, Nd, Co, oxides thereof, andcombinations thereof, whereby the core or framework is provided with atooth color corresponding to a natural tooth shade and the core orframework has a flexural strength of at least about 800 MPa whensintered to at least 98% of its theoretical density. The overlay may beporcelain and can be fused to the core or framework resulting in a finaltooth-like appearance.

According to a further aspect, the present invention provides a methodof forming a dental article, the method comprising: providing a firstuncolored powder; combining at least one first coloring agent and asecond powder thereby forming a first pigment powder; mixing the firstuncolored powder and the first pigment powder, thereby forming a mixedpowder; pressing the mixed powder to form a pressed body; and firing thepressed body; thereby producing a dental article comprising a colorcorresponding to a predetermined natural tooth shade, and a flexuralstrength of at least 800 MPa when sintered to at least 98% of itstheoretical density.

According to an additional aspect, the method described above mayfurther comprise: combining at least one second coloring agent and thesecond powder thereby forming a second pigment powder; mixing the firstuncolored powder, the first pigment powder, and the second pigmentpowder, thereby forming the mixed powder.

According to yet an additional aspect, the method described above mayfurther comprise: combining at least one third coloring agent and thesecond powder thereby forming a third pigment powder; mixing the firstuncolored powder, the first pigment powder, and the second pigmentpowder, and the third pigment powder, thereby forming the mixed powder.

According to another aspect, the white powders and pigment powdercombinations are made into liquid suspensions useful forinjection-molding or rapid-prototyping feedstocks, that have a solidscontent of 2 to 90 wt. %. These suspensions or feedstocks are used toform dental articles via a number of techniques including gel casting,slip casting, freeze casting, electrophoretic deposition, injectionmolding, or rapid prototyping (also known as solid freeformfabrication). “Rapid prototyping” is the generic term for net-shapemanufacturing of materials into complex shapes and includes,stereolithography, photo-stereolithography, digital light processing(DLP), selective area laser deposition, selective laser sintering (SLS),electrophoretic deposition (EPD), robocasting, fused deposition modeling(FDM), laminated object manufacturing (LOM), or 3-D printing, asdescribed in greater detail in US Patent Application Publication No.2005/0023710, which is incorporated hereby by reference.

The pigment powders can be colored to the three primary colors, i.e.,yellow, pink and grey/blue, or colors that can be effectively used inlieu of primary colors in dental color space, i.e., brown orpinkish-mauve, in place of pink.

Additionally, we have discovered that the colorant Cr (pinkish), can beused in combination with other potent colorants, Pr (yellow), and Co(blueish grey), to achieve tooth colored zirconia. Remarkably, the totalcolorant amount required is on the order of only 0.035 wt. % (0.0063mol. %).

In addition, according to the present invention, Cr has been found to bea potent coloring additive that, surprisingly, results in apinkish-mauve color for sintered 3Y-TZP bodies with small Cr additions(on the order of 0.003 wt. % (0.005 wt. % Cr₂O₃)).

BRIEF DESCRIPTION OF THE DRAWING FIGURES

The following detailed description of preferred embodiments can be readin connection with the accompanying drawing in which:

FIG. 1 is a cross-sectional illustration of an example of a dentalarticle formed according to the principles of certain embodiments of thepresent invention.

DETAILED DESCRIPTION

According to certain aspects of the present invention, there is provideda sintered ceramic body which is doped with or otherwise contains one ormore coloring agents. The one or more coloring agents are selected so asto provide the sintered ceramic body with a desired color byincorporating a relatively small amount of the coloring agents into thecomposition of the sintered ceramic body. The relatively small amount ofthe addition of coloring agents advantageously minimizes any adverseimpacts that the coloring agents might have on the properties of thesintered ceramic body.

According to the present invention, the ceramic body can take anysuitable form, shape, or geometry. According to one embodiment, asintered ceramic body is provided in the form of a dental article. Thus,the identity and amount of one or more coloring agents incorporated intothe composition of the sintered ceramic body are chosen so as to providethe sintered ceramic body with a final color corresponding to a desirednatural tooth color or shade. A number of different dental articles arecontemplated. For example, dental articles formed according to theprinciples of the present invention can include: blocks or blankssuitable for subsequent machining; a prefabricated shape; supports orframeworks for a dental restorations; a coping; pontic; denture teeth;space maintainers; tooth replacement appliance; orthodontic retainer;denture; post jacket; facet; splint; cylinder; pin; connector; crowns;partial crowns; veneers; onlays; inlays; bridges; fixed partialdentures; Maryland Bridges; implant abutment. According to anillustrative example, a dental restoration formed according to theprinciples of the present invention is illustrated in FIG. 1. Asillustrated therein, a dental restoration 10 can comprise a support orframework 20 in the form of a sintered ceramic body having aconcentration containing one or more coloring agents according to theprinciples of the present invention, to which is bonded to an overlaymaterial 30. The support or framework 20 can be formed of any suitablebase ceramic material described herein, such as a stabilized yttriatetragonal zirconia polycrystalline material (YTZP), and one or morecoloring agent having an identity and an amount as described furtherbelow. The overlay 30 can likewise be formed of any suitable overlaymaterial, for example, an overlay of zirconia-porcelain material can beutilized.

According to one optional aspect of the present invention, the sinteredceramic body can comprise porous zirconia (e.g., YTZP) blocks or blanks,which are preshaded, optionally by any of the techniques describedherein, and can optionally be processed by CAD/CAM techniques, thenfinally sintered to form colored dental frameworks of high strength. Theterm “blocks” and “blanks” are not intended to limit the geometry of thearticles of the present invention. Any suitable CAD/CAM technique may beutilized in connection with the present invention. For example, suchtechniques are described in U.S. Pat. No. 7,011,522, which isincorporated herein by reference, in its entirety. The blocks or blankscan be in the as-pressed green state (with binder), or pre-sinteredstate (with binder removed). The blocks can have a pore volume of 40 to80%, and can be sinterable to at least 99% of theoretical densityyielding grain sizes of 0.2 to 1.5 μm, at sintering temperatures of 1150to 1550° C., average flexural strengths in excess of 800 MPa, optionallyin excess of 900 MPa, and optionally in excess of 1,000 MPa, whensintered to at least 98% of its theoretical density, are attainable. Theblocks are machinable and are characterized by isotropic shrinkageduring the sintering process enabling their processing by CAD/CAMtechniques into dental restorations of high strength and excellent fit.

The ceramic body can comprise any suitable composition to which one ormore coloring agents can be added. According to certain optionalaspects, the base ceramic to which one or more coloring agents is addedcan comprise a stabilized ceramic. For example, the base ceramic cancomprise a yttria stabilized tetragonal zirconia polycrystalline ceramicmaterial (YTZP), calcia stabilized zirconia, magnesia stabilizedzirconia, and/or ceria stabilized zirconia, all of which can be obtainedcommercially.

The base ceramic material can be doped or combined with one or morecoloring agents. For example, the base ceramic composition can be dopedwith no more than 0.15 wt. %, optionally no more than 0.10 wt. %,optionally no more than 0.08 wt. %, or optionally no more than 0.07 wt.% of coloring agent(s) or additive(s). The above-mentioned amountsreferred to the amounts of either the elemental, ionic, and/or oxideform of the agent(s) contained in the sintered ceramic body. The one ormore coloring agents or additives can be selected from: Tb, V, Ce, Pr,Cr, Co, Nd, Ni, Cu, Ho, oxides thereof, and combinations thereof.Optionally, the one or more coloring agents can be selected from: Pr,Tb, Cr, Nd, Co, oxides thereof, and combinations thereof. The coloringagents can comprise: at least Pr and/or an oxide thereof; at least Pr,Cr, and/or oxides thereof; Pr, Cr, Co and/or oxides thereof; and atleast Tb, Nd, and/or oxides thereof. Optionally, the coloring additivescan consist essentially of: Pr and/or an oxide thereof; Pr, Cr, and/oroxides thereof; Pr, Cr, Co and/or oxides thereof; and Tb, Nd, and/oroxides thereof.

A sintered ceramic body including a small amount of one or more of thecoloring agents, as described above can additionally possess goodphysical properties, such as a high flexural strength with a weibullmodulus greater than 10. For example, a sintered ceramic body formedaccording to the present invention may have an average flexural strengthin excess of 800 MPa, optionally in excess of 900 MPa, and optionally inexcess of 1,000 MPa. The flexural strength is measured per aconventional three-point bend test.

The resulting colors of the as-sintered articles are suitable for dentalrestoration frameworks that can be overlaid with a suitable overlaymaterial, such as a zirconia-porcelain system, to achieve tooth-coloredshades for the finished restoration.

The present invention is also directed to methods or techniques forcoloring sintered ceramic bodies. According to one illustrativetechnique, an uncolored base ceramic powder can be combined with one ormore additional powders which contain one or more coloring agents oradditives. These additional powders can be termed “pigments” or “pigmentpowders.” Once these powders have been combined, they can then beprocessed according to conventional techniques to produce a finishedsintered body possessing the desired coloration, and mechanicalproperties.

The uncolored base ceramic powder can have any suitable composition,such as including any of the compositions described above for baseceramic materials (e.g., YTZP). Similarly, the one or more coloringagents or additives can also comprise any one, or combination of, thecoloring agents or additives described above. According to theprinciples of the present invention, the amount of the one or morecoloring agents contained in the pigment powders, as well as theproportions of the uncolored base ceramic and pigment powders, arecalculated so as to provide a finished sintered body having a desiredtotal quantity of coloring agents contained therein. This calculationcan be performed according to conventional techniques familiar to thoseskilled in the art, and which are further elucidated by reference to thefollowing examples.

As pointed out in U.S. Pat. No. 6,030,209, the shading of dentalporcelain to achieve tooth colors typically relies on blending ofyellow, pink, grey/blue pigments (i.e., primary colors) with the “white”porcelain powder to achieve the desired tooth colors. Surprisingly, thismodel also seems appropriate for shading of zirconia, as demonstrated inthe following examples.

Examples 1 to 8 below illustrate how coloring formulations can bedeveloped via immersion of pre-sintered blanks in solutions comprisingcoloring additives. Example 4 also illustrates sintered bodies that havebeen provided with colors using a relatively small amounts of coloringagent. Examples 9 toll illustrate combining YTZP powder with one or morecoloring additives by immersion of as-received powder in solutionscomprising coloring additives in ionic or complex form. Examples 12 and13 illustrate combining YTZP powder with one or more coloring additivesby combining YTZP powder and one or more pigment powders that have beendoped with at least one coloring additive.

In alternative embodiments of the present invention the doped powder isfabricated by introduction of coloring additives as individual oxides orother precursor forms before, during, or after one of the stages of themanufacturing of said powder such as hydrolysis, drying, calcination,milling, or spray drying processing steps. These precursor forms includebut are not limited to individual or complex oxides, salts, inorganic ororganic and organo-metallic compounds (and combinations thereof) addedin the form of aqueous or nonaqueos solutions, emulsions, dispersions,gels and particulates. All concentrations that are referred to in theexamples are by weight percentage.

The salts used in the examples are all commercially available and wereobtained from Alfa Aesar, Ward Hill, Mass. The zirconia powders thatwere used in the examples were the commercially available 3Y-TZP grades,TZ-3YB-E, and TZ-3YB, from Tosoh USA, Inc., Grove City, Ohio. TheTZ-3YB-E grade contains approximately 0.25 wt. % alumina, and the TZ-3YBgrade is essentially alumina-free. For the examples in which it wasused, the TZ-3YB grade is explicitly indicated. All other examples usedthe TZ-3YB-E grade. All firing cycles were done in an air atmosphere.The densities and flexural strengths reported for select sinteredspecimens were measured by the Archimedes method, and per ISO 6872,respectively. Color was evaluated as necessary, both visually, by acertified dental technician, and measured on a white background using aColorTec-PSM™ spectrophotometer from ColorTec™, Clinton, N.J. The colorparameters were read in reference to D65/10² illuminations standard.Fluorescence in the visible light range was evaluated using a modelUVL-56 BLAK-RAY® Lamp, Longwave UV-365 nm, ultraviolet light box fromUVP, Upland, Calif.

Example 1

Salts of Pr, Ce, Tb, V, Fe, Er, Cr, Eu, Ho, Co, Nd, Ni, and Cu weredissolved in distilled water in the proportions shown in Table 1.Zirconia discs, 27 mm diameter×2.75 mm thick, were pressed (10 MPa,uniaxial) from TZ-3YB-E powder and subsequently fired by heating at 1°C./m to 700° C., holding for 2 h (debinderization), followed by heatingat 4° C./m to 1100° C., holding for 2 h (presintering), and then coolingat 4° C./m to ambient. The presintered density was approximately 3.15g/cc. Presintered zirconia discs were immersed in the salt solutions for10 minutes, removed and then fired by heating at 4° C./m to 150° C.,holding for 2 h (drying), followed by heating at 4° C./m to 1500° C.,holding for 2 h (sintering), and then cooling at 4° C./m to ambient. Thesame firing was also given to a “control”, i.e., a presintered disc thathad not been immersed in solution. The resulting colors are listed inTable 1, and include yellow, pinkish-mauve (where “mauve” is defined asa “moderate purple”), pink, grey, blue and green. The control fired to atranslucent white color.

TABLE 1 Element Solution Color Pr 0.5% Praseodymium (III) acetatehydrate Yellow Ce 10% Ce(III) nitrate Yellow Tb 0.05% terbium(III)chloride hexahydrate Yellow-orange V 0.1% vanadium(IV) fluoride YellowFe 1% Iron(II) chloride Yellow Er 10% Erbium (III) chloride hexahydrateLight Pink Cr 0.05% Cr(III) chloride hexahydrate Mauve Eu 10%Europium(III) Chloride Hydrate White Ho 10% Ho(III) chloride Yellow/pinkCo 0.1% Co(II) chloride Grey Ni 0.5% Ni(II) chloride Green Cu 0.5%Cu(II) acetate Green Nd 5% Nd(III) chloride hydrate Light blue

Example 2

Solutions of Tb(III) chloride hexahydrate and V(IV) fluoride, ofdifferent concentrations were prepared (Table 2). Pre-sintered zirconiadiscs were immersed in the solutions and fired as per Example 1. Theresults are shown in Table 2 and demonstrate that the intensity of thecolor achieved, yellow, can be controlled by the solution concentration.Specifically, one can increase the yellow intensity by increasingsolution concentration.

TABLE 2 Solution Color Tb(III) chloride hexahydrate, % 0.005 Pale yellow0.01 medium yellow 0.05 Yellow V(IV) fluoride, % 0.005 pale yellow 0.01pale yellow 0.10 yellow

Example 3

Solutions of Praseodymium (III) acetate hydrate and Cr(III) chloridehexahydrate, of different concentrations were prepared (Table 3).Pre-sintered zirconia discs were immersed in the solutions and fired asper Example 1. Some discs were sintered in the as-pre-sintered state,and were the controls. Flexural strengths were measured for as-firedsurfaces using the 3-point-bend test configuration. The results areshown in Table 3. Again, the results show that the intensity of thecolor achieved, can be controlled by the solution concentration.Additionally, coloring with 0.01% Pr-acetate and 0.01% Cr-chloride doesnot appear to adversely affect densification or flexural strength, i.e.,the densities and flexural strengths of Pr- and Cr-colored specimens wasstatistically the same as for the control.

TABLE 3 Density Solution Color (g/cc) Flexural Strength (MPa) % Pr(III)acetate hydrate 1 orange — — 0.25 dark yellow 6.00 — 0.10 medium yellow6.05 1,106 ± 327 (n = 8) 0.05 yellow 6.08 — 0.01 pale yellow — — %Cr(III) chloride hexahydrate 0.10 dark pinkish- 6.07 1,099 ± 184 (n =10) mauve 0.05 medium 6.03 — pinkish-mauve 0.01 light pinkish- — — mauveNone (control) white 6.07 1,153 ± 261 (n = 8)

Example 4

Three solutions were prepared by dissolving Praseodymium(III) acetatehydrate, Chromium(III) chloride hexahydrate, and Co(II) chloride indistilled water in the proportions shown in Table 4. Pre-sinteredzirconia discs were immersed in the solutions and fired as perExample 1. The discs were thinned to 0.5 mm and the surface color wasevaluated. The results are shown in Table 4 along with the calculatedconcentrations of the coloring additive ions as calculated based on thesolution concentration and the assumption that during immersion, thesolution completely filled the pore volume of the pre-sintered bodies.

TABLE 4 % % Cr(III) Total Concentra- Pr(III) chloride tion of ColoringFlexural acetate hexa- % Co(II) Density Ions (calculated) Strength Shadehydrate hydrate chloride (g/cc) CIE L, a, b wt. % (MPa) 1 0.025 0.025 06.07 81.78, 1.12, 18.05 0.0026 n/a 2 0.008 0.002 0 n/a 87.4, −0.37,12.36 0.0007 n/a 3 0.024 0.005 0.005 6.07 ± 0.01 86.55, 0.34, 9.590.0024 921 ± 203 (n = 12)

Shades 1, 2 and 3 did not fluoresce under UV illumination. Shades 1, 2are considered appropriate core shade for some of the Vita Classic A, Cand D shades, respectively. These results show that YTZP can be shadedvia combinations of Pr, Cr and Co, to achieve coloration that isappropriate for dental frameworks.

Example 5

Pre-sintered 25×10×2.5 mm³ TZ-3YB bars were machined by hand into a“shade tab” geometry using a dental handpiece with a diamond bur. Thisentailed shaping one end of the bar into a veneer that was approximately0.6 mm in thickness. The shaped bar was immersed for 10 minutes in thecoloring solution corresponding to Shade 1 of Table 4, and fired as perExample 1. The as-sintered shade tabs were nearly fully dense (6.05g/cc), translucent, with a thickness of approximately 0.5 mm for theveneer portion. The veneer portion was overlayed with the zirconiaporcelain, OPC 3G, Pentron Ceramics Inc., Somerset, N.J., to achievetooth colored shade of approximately Al of the Vita Classic shade guide.

Example 6

A colored shade tab prepared as per Example 5 was overlayed withporcelain as per Example 5, to achieve a tooth colored shade ofapproximately A2 of the Vita Classic guide.

Example 7

A pre-sintered shade tab prepared as per Example 5 was immersed for 10minutes in the coloring solution corresponding to Shade 3 of Table 4,and fired as per Example 1. The resulting fully sintered specimen wasoverlayed with porcelain as per Example 5, to achieve a tooth coloredshade of approximately D3 of the Vita Classic shade guide.

Example 8

A 0.25 wt. % solution of Praseodymium (III) acetate hydrate in distilledwater was prepared. Pre-sintered zirconia discs, 27 mm dia.×2.75 mmthick, and pellets 16 mm diameter by 10 mm tall, were prepared as perExample 1. These were immersed in the solutions for a range of timesfrom 10 minutes up to 144 h, and fired as per Example 1. The resultingsurface coloration was an orangish-yellow, and was approximately samefor all specimens. The specimens were cross-sectioned revealing that thecoloring depth increased with immersion time. The cores of all thespecimens were white in color.

TABLE 5 Approximate Depth of immersion time coloration (mm) 10 min 0.252 h 0.5 72 h 2.5 144 h 3

Example 9

A 0.25 wt. % solution of Praseodymium(III) acetate hydrate in distilledwater was prepared. The solution was added to TZ-3YB-E powder in aone-to-one ratio, by weight. The powder+solution combination was stirredthoroughly and then dried by heating to 150° C. and holding for 4 h. Thedried powder was screened through a 170 mesh (90 μm) nylon screen, andpressed into discs as per Example 1. The discs were debinderized byheating at 1° C./m to 700° C., and holding for 5 h, followed by heatingat 4° C./m to 1500° C., and holding for 2 h, to sinter the bodies, andthen cooling at 1° C./m to ambient. This resulted in a dark-yellowcolored body that was colored through the thickness and had a density of6.07 g/cc. This example demonstrates that colored TZP blocks can bemanufactured by immersing the powder in the coloring salt solution priorto drying followed by compaction.

Example 10

Solutions of Praseodymium(III) acetate hydrate and Chromium(III)chloride hexahydrate in distilled water were prepared according to Table6.

TABLE 6 Pr(III) acetate hydrate Cr(III) chloride Solution (wt. %)hexahydrate (wt. %) Distilled Water 1 0.5 0 Balance 2 0 0.05 Balance 3 00 Balance

A third “solution”, 100% water, served as the control. The solutionswere individually added to TZ-3YB-E powder in a 8-to-25 ratio, byweight, and the combinations were thoroughly mixed. The resulting blendswere subsequently freeze-dried for approximately 12 hours and screenedthrough a 250 mesh (55 micron) nylon screen to yield a free-flowingpowder. Discs, 27 mm diameter by 1.2 mm thick, were pressed from thesepowders as per Example 1, and fired by heating at 1° C./m to 700° C.,and holding for 2 h (debinderization step), followed by heating at 4°C./m to 1500° C., and holding for 2 h (sintering step), and then coolingat 4° C./m to ambient. The results are shown in Table 7.

TABLE 7 Nominal coloring dopant content (wt. %) Bend Pr Cr Color DensityStrength Solution (Pr₆O₁₁) (Cr₂O₃) Visual CIE L, a, b (g/cc) (MPa) 10.0709 0 Yellow 82.15, 2.93, 37.12 6.09 1152 ± 208 (0.0856) 2 0 0.0031Mauve 81.49, 1.67, 7.67 6.05  997 ± 119 (0.0046) 3 0 0 white 88.76,−0.14, 3.69 6.07 1026 ± 178

These results show that doping of TZ-3YB-E with approximately 0.07 wt. %Praseodymium(III) yields a yellow sintered body with no compromise indensity and strength. Also, they demonstrate that doping withapproximately 0.003 wt. % of Cr(III) yields a sintered body that ispinkish-mauve in color with no compromise in density and strength. Forall cases, coloration was uniform and was through the thickness of thesintered samples.

Example 11

Three solutions of Praseodymium(III) acetate hydrate+Chromium(III)chloride hexahydrate in distilled water were prepared according to Table8.

TABLE 8 Pr(III) acetate hydrate Cr(III) chloride Solution (wt. %)hexahydrate (wt. %) Distilled Water 4 0.0625 0.025 Balance 5 0.18750.03125 Balance 6 0.125 0.0625 Balance

These solutions were used to process TZ-3YB-E powders into sintered dicsas per Example 10. Color and fluorescence evaluation was done as perExample 4 on discs that had been thinned to 0.5 mm. Visual colorevaluation entailed comparing the colored discs to a 3M™ ESPE™LAVA™FrameShade Tabs set available from Issaquah Milling Center, Issaquah, Wash.The set consists of 0.5 mm thick sintered zirconia specimens that hadbeen shaded with the 3M™ ESPE™LAVA™ Frame Shade Dyeing Liquids, 3MCenter, St. Paul, Minn., to the core shades: FS1, FS2, FS3, FS4, FS5,FS6 and FS7. The results are presented in Table 9.

TABLE 9 Color Nominal coloring Visual dopant (vs. content (wt. %) LAVA ™Pr Cr frame Density Solution (Pr₆O₁₁) (Cr₂O₃) shades) CIE L, a, b (g/cc)4 0.0089 0.0016 Close to FS2 83.99, −0.55, 6.06 (0.0107) (0.0023) 15.815 0.0267 0.0019 Close to FS3 85.19, −1.44, 6.06 (0.0322) (0.0028) 21.326 0.0177 0.0047 Matches FS7 81.6, −0.04, 6.12 (0.0214) (0.0069) 18.85

Tooth colorations were achieved, and for all cases the coloration wasuniform and was through the thickness of the sintered samples.Additionally, the tooth colored specimens did not fluoresce under UVillumination. These results demonstrate that the coloring dopants, Prand Cr, can be used in combination to achieve shades appropriate forachieving finished restorations that are tooth-colored. It is noteworthythat the dopant levels required are of very low concentrations, e.g.,Pr<approximately 0.030% and Cr<approximately 0.005%.

Example 12

Solutions of 0.75 wt. % Praseodymium(III) acetate hydrate and 0.25 wt. %Cr(III) chloride hexahydrate, in distilled water were prepared. Thesesolutions were individually mixed with TZ-3YB-E powder, dried andscreened, as per Example 10. This yielded powders nominally doped with0.1063% Pr and 0.0156% Cr, respectively. The doped powders were thencombined with as-received TZ-3YB-E powder in the following properties:8.3725% Pr-doped+10.2564% Cr-doped+81.3711% as-received TZ-3YB-E powder,and blended for 15 minutes using a paint shaker. (The proportions werecalculated to give the same bulk nominal Pr and Cr concentration asSolution 4 of Table 9.) Several sintered discs were prepared from thepowders as per Example 10, and their color was evaluated as per Example11. Remarkably, visually, the color of the discs was uniform when viewedat 1×, 4× and 8× magnifications. One of the discs was thinned to 0.5 mmin thickness and CIE L*, a*, b* color coordinates of 84.21, −0.85,18.25, respectively, were determined. Visually this specimen matchedLAVA core shade FS2. Also, it did not fluoresce under UV illumination.Strength was measured to be 1,161±178 MPa (n=8).

Example 13

The doped powders of Example 12 were combined with as-received TZ-3YB-Epower in the following proportions: 16.651% Pr-doped+30.1782%Cr-doped+53.2208% as-received TZ-3YB-E powder, and blended for 15minutes using a paint shaker. (These proportions were calculated to givethe same bulk nominal Pr and Cr concentration as Solution 6 of Table 9.)Several sintered discs were prepared from the powders as per Example 10,and their color was evaluated as per Example 11. Like in Example 12,visually, the color of the discs was uniform. One of the discs wasthinned to 0.5 mm in thickness and CIE L*, a*, b* color coordinates of80.64, −0.41, 19.37, respectively, were determined. Visually thisspecimen matched LAVA core shade FS7 and did not fluoresce under UVillumination. Strength was measured to be 1,025±178 MPa (n=7).

Example 14

Zirconia powder with a composition corresponding to Solution 6 of Table9 is pressed into cylindrical blocks that are 2.0 cm dia.×4.0 cm long.This is done with a wet-bag cold isostatic press at pressure of 200 MPausing polyurethane tooling. The blocks are heated at 1° C./m to 700° C.,and held for 10 h (debinderization), followed by heating at 4° C./m to1000° C., and holding for 2 h (presintering), and then cooling at 4°C./m to ambient. The green density of the pre-sintered blocks isapproximately 3.15 g/cc.

Using the laser scanner, D-250™ 3D Scanner, 3Shape A/S Copenhagen,Denmark, models of a single-unit and 3-unit-bridge preparations arescanned to create a 3D digital model which are saved as STL files. Usingthese files, the dental CAD software, DentalDesigner™, 3Shape A/SCopenhagen, Denmark is used to design the corresponding frameworks. The3D models are saved as a STL files. These are transferred to acommercial CAM device with the ability to enlarge 3D digital model bythe appropriate enlargement factor. Using an enlargement factor ofapproximately 1.243, which is inputted into the CAM software, thepresintered blocks are machined into an oversized single-unit and3-unit-bridge frameworks. The as-machined frameworks are sintered as perExample 10. The resultant sintered frameworks are of high density(approximately 6.05 g/cc), translucent, and uniformly colored with ashade closely matching LAVA FS7. The fit of the as-sintered frameworksonto the starting models is determined to be acceptable. This isindicative of isotropic shrinkage during the sintering step. Theas-sintered frameworks are overlayed with Noritake Cerabien CZRPorcelain, Noritake Company, Inc., Fairlawn, N.J., to achieve a finalVITA classic shade D2. The fit of the finished restorations to thestarting models are determined to be acceptable. Shades and fit areevaluated by a certified dental technician.

Example 15

Zirconia powder prepared as per Example 12 is processed into cylindricalCAD/CAM blocks as per Example 14. The blocks are then processed intosintered single-unit and 3-unit-bridge frameworks as per Example 14. Theresultant sintered frameworks are of high density (approximately 6.05g/cc), translucent, and uniformly colored with a shade closely matchingLAVA FS2. The fit of the as-sintered frameworks onto the starting modelsis determined to be acceptable. The as-sintered frameworks are overlayedwith Noritake Cerabien CZR Porcelain, Noritake Company, Inc., Fairlawn,N.J., to achieve a final VITA classic shade A2. The fit of the finishedrestorations to the starting models are determined to be acceptable.Shades and fit were evaluated by a certified dental technician.

Numbers expressing quantities of ingredients, constituents, reactionconditions, and so forth used in this specification are to be understoodas being modified in all instances by the term “about”. Notwithstandingthat the numerical ranges and parameters setting forth, the broad scopeof the subject matter presented herein are approximations, the numericalvalues set forth are indicated as precisely as possible. For example,any numerical value may inherently contains certain errors resultingfrom the standard deviation found in their respective measurementtechniques or in rounding off of measured values. None of the elementsrecited in the appended claims should be interpreted as invoking 35U.S.C. §112, ¶6, unless the term “means” is explicitly used.

Although the present invention has been described in connection withpreferred embodiments thereof, it will be appreciated by those skilledin the art that additions, deletions, modifications, and substitutionsnot specifically described may be made without department from thespirit and scope of the invention as defined in the appended claims.

1. A dental article comprising: yttria stabilized tetragonal zirconiapolycrystalline ceramic; and no more than about 0.15 wt. % of one ormore coloring agents comprising one or more of: Pr, Tb, Cr, Nd, Co, Ni,oxides thereof, and combinations thereof, whereby the dental article isprovided with a color corresponding to a natural tooth shade; whereinthe dental article has a flexural strength of at least about 800 MPawhen sintered to at least 98% of its theoretical density.
 2. The dentalarticle of claim 1, wherein the article has a strength distributioncharacterized by a Weibull modulus of greater than
 10. 3. The dentalarticle of claim 1, wherein the article further comprises less thanabout 0.1 wt. % aluminum oxide.
 4. The dental article of claim 1,wherein the article has a flexural strength of at least about 1000 MPawhen sintered to at least 98% of its theoretical density.
 5. The dentalarticle of claim 1, wherein the article comprises at least one of: ablock or blank, a prefabricated shape, a support or framework for adental restoration, a coping, pontic, denture teeth, space maintainers,tooth replacement appliance, orthodontic retainer, denture, post jacket,facet, splint, cylinder, pin, connector, a crown, a partial crown, aveneer, an onlay, an inlay, a bridge, fixed partial dentures, a Marylandbridge, an implant abutment or whole implant.
 6. The dental article ofclaim 1, wherein the one or more coloring agents comprise Pr and/oroxides thereof.
 7. The dental article of claim 1, wherein the one ormore coloring agents comprise Cr and/or oxides thereof.
 8. The dentalarticle of claim 1, wherein the one or more coloring agents comprise Coand/or oxides thereof.
 9. The dental article of claim 1, wherein the oneor more coloring agents comprise Pr, Cr, and/or oxides thereof.
 10. Thedental article of claim 1, wherein the one or more coloring agentsconsist essentially of Pr, Cr, and/or oxides thereof.
 11. The dentalarticle of claim 1, wherein the one or more coloring agents comprise Pr,Cr, Co and/or oxides thereof.
 12. The dental article of claim 1, whereinthe one or more coloring agents consist essentially of Pr, Cr, Co and/oroxides thereof.
 13. The dental article of claim 1, wherein the one ormore coloring agents comprise Tb, Nd and/or oxides thereof.
 14. Thedental article of claim 1, wherein the one or more coloring agentsconsist essentially of Tb, Nd and/or oxides thereof.
 15. The dentalarticle of claim 1, wherein the article comprises no more than about0.10 wt. % of the one or more coloring agents.
 16. The dental article ofclaim 9, wherein the article comprises no more than about 0.08 wt. % ofthe one or more coloring agents.
 17. The dental article of claim 10,wherein the article comprises no more than about 0.07 wt. % of the oneor more coloring agents.
 18. The dental article of claim 1, wherein thedental article has a flexural strength of at least about 900 MPa whensintered to at least 98% of its theoretical density.
 19. The dentalarticle of claim 18, wherein the dental article as a flexural strengthof at least about 1200 MPa when sintered to at least 98% of itstheoretical density.
 20. The dental article of claim 1, wherein theyttria stabilized tetragonal zirconia polycrystalline ceramic istranslucent.
 21. A dental restoration comprising: a core or frameworkcomprising: yttria stabilized tetragonal zirconia polycrystallineceramic; and no more than about 0.15 wt. % of one or more coloringagents comprising one or more of: Pr, Tb, Cr, Nd, Co, Ni, oxidesthereof, and combinations thereof, whereby the core or framework isprovided with a color corresponding to a natural tooth shade; whereinthe core or framework has a flexural strength of at least about 800 MPa;and an overlay bonded to the core or framework.
 22. The dentalrestoration of claim 21, wherein the restoration comprises at least oneof: a crown, a partial crown, a veneer, an onlay, an inlay, a bridge,fixed partial dentures, a Maryland bridge, an implant abutment or wholeimplant.
 23. The dental restoration of claim 21, wherein the overlay isbonded to the core or framework by firing, fusing, sintering orpressing.
 24. The color dental restoration of claim 21, has CIE L*, a*,b* color coordinates within CIE L*, a*, b*color space region associatedwith tooth colors.
 25. The dental restoration of claim 21, wherein theoverlay comprises porcelain.
 26. The dental restoration of claim 21,wherein the yttria stabilized tetragonal zirconia polycrystallineceramic is translucent.